title: Intramolecular photoelectron diffraction in the gas phase.
abstract: We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.
authors.affiliation: Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.
authors.forename: K
authors.initials: K
authors.lastname: Ueda
authors.forename: C
authors.initials: C
authors.lastname: Miron
authors.forename: E
authors.initials: E
authors.lastname: Plésiat
authors.forename: L
authors.initials: L
authors.lastname: Argenti
authors.forename: M
authors.initials: M
authors.lastname: Patanen
authors.forename: K
authors.initials: K
authors.lastname: Kooser
authors.forename: D
authors.initials: D
authors.lastname: Ayuso
authors.forename: S
authors.initials: S
authors.lastname: Mondal
authors.forename: M
authors.initials: M
authors.lastname: Kimura
authors.forename: K
authors.initials: K
authors.lastname: Sakai
authors.forename: O
authors.initials: O
authors.lastname: Travnikova
authors.forename: A
authors.initials: A
authors.lastname: Palacios
authors.forename: P
authors.initials: P
authors.lastname: Decleva
authors.forename: E
authors.initials: E
authors.lastname: Kukk
authors.forename: F
authors.initials: F
authors.lastname: Martín